Theoretical Investigations of C–O Activation in Biomass

Abstract: This thesis focuses on using computational chemistry approaches to study how biobased molecules interact with both homo- and heterogeneous catalysts. The reaction mechanisms of such transformations have also been studied.The first section comprises studies of interactions between organic molecules and a heterogeneous catalyst in the palladium-catalyzed depolymerization of models of lignin derivatives. From experiments, it was proposed that a keto intermediate and its enol tautomer play a significant role in the β-O-4′ bond cleavage. The study in the first section of this thesis has been divided into three parts. First, simplified models of the keto intermediate and its enol tautomer were used to investigate the adsorption to a Pd(111) surface. By using a combination of periodic density functional theory (DFT) calculations and a constrained minima hopping method, the most stable adsorption which is the so-called global minimum, was found to be an enol adsorbed to the surface.In the second part, the study was expanded to cope with models of lignin which were used in experiments. In addition, we studied the effect of adsorbate coverage, where two different Pd(111) super cells were compared. The optimizations were performed via dispersion-corrected density functional theory (DFT-D3). The molecules were found to bind more strongly to the surface at low coverages. These results support the experimental data and show that the tautomerization has an important role during lignin depolymerization. The third part relates to using a multilevel procedure to study the interaction of fragments derived from lignin depolymerisation with a palladium catalyst in a solvent mixture. Specifically, QM calculations and MD simulations based on the ReaxFF approach were combined to explore the reaction mechanisms occurring on Pd surfaces with lignin derivatives obtained from a solvolysis reaction. The strongest adsorptions were found to be between the aromatic rings and the Pd surfaces.The second section focuses on a Brønsted acid-catalyzed nucleophilic substitution of the hydroxyl group in alcohols. Experimentally, phosphinic acid (H3PO2) was found to be an excellent catalyst for the direct intramolecular substitution of non-derivatized alcohols proceeding with good to excellent chirality transfer. In this section, benzylic alcohols with internal O-, N-, and S-centered nucleophiles were used in the calculations. By using a hybrid functional method, we found a bicyclic transition state where the proton of the H3PO2 protonates the leaving hydroxyl group, and the oxo-group of the same catalyst partially deprotonates the nucleophile. The transition state energies for the reactions were determined computationally. The calculations support an SN2 mechanism, which corresponds to the experimental data where inversion of the stereogenic carbon was observed.